SU765302A1 - Nonpolar rubber-based vulcanized rubber mixture - Google Patents

Description

This invention relates to the rubber industry, in particular to the development of a rubber mixture based on non-polar rubber. The known rubber mixture based on non-supportive rubber, including a desiccant, a vulcanization activator, a vulcanizing agent, a vulcanization accelerator, a filler and a plasticizer (oil PN-6), for example, in a ratio of 60: 1.2: 3: 1.4: 0.9 : 29: 4,5 l. Rubber obtained from a known mixture, have unsatisfactory physico-mechanical and operational properties and cold resistance. In addition, the rubber mixture has an increased cost. The purpose of the invention is to increase the frost resistance, the physicomechanical and operational properties of rubber from a rubber mixture based on non-virgin rubber, as well as cheaper rubber. The goal is achieved by the fact that a rubber mixture based on non-polar rubber, including a cispergator, a vulcanization activator, a vulcanizing agent, a vulcanization accelerator, a filler and a plasticizer, as a plasticizer contains base hydrocracking oil with a kinematic viscosity of 3.5-25 eats at + 5 ° C in the following ratio of components, wt.%: 55.1 O-62.7 O Rubber 1.11-1.70 Disperser Vulka activator 1, 67-3.11 low Vulcanizing 1,10-2,49 agent Accelerator Vulka 0, 84-2 , 71 nizatsiya Base oil 2,80-11,14 hydrocracking Else Filler Properties of base oil hydrocracking are shown in Table. 1 a l l and c 1 Baa oil Indicators for hydrocracking Kinematic viscosity from 3.5 to 25 at 50 ° C, eats Flash point, C n / n + 160 ° C Pour point, c / v -45 ° C Glass temperature76

Example 1. Preparing mixtures based on isoprene rubber SKI-3 using the well-known PNGb oil and the proposed hydrocracking base oil as a plasticizer.

The recipe for mixtures (in weight ..%) is given in table. 2. A control mixture without a plasticizer was also manufactured.

Table 2 2 Hydrocracking base oils are characterized by very large variations in properties depending on the distillation temperature of the target fraction. For example, their temperature, flares can reach up to + 24 ° C, the freezing point to -65 ° C, and the glass transition temperature to -100 ° C. The invention is illustrated by the example.

Rubber SKI-360,7959, ОО57,31 Stearic acid 1,221,181,15 Altax0,910,88О, 86 Zinc oxide1,821,771,72 Soot PM-10О30,4О29,528,65 Base hydrocracking oil BMG-3,53,04 5,908 , 60 Oil ПН-6 ... Сера1,82 1,771,72

 The digit after the letters BMG means the kinematic viscosity of the mask in eats at +50 C, and, respectively, the BMG-3.5 has a kinematic viscosity of 3.5 eats at +50 C, the BMG-22- respectively 22 eats poi + 5O С and so on. d. 5.7160.7959, ОО57.31 55.71 62.7О 1.1111.221.181.15 1.11 1.25 0.840.910.880.86 0.84 O, 94 1.671.821.771.72 1.67 1.88 27.86OZ, 4O29.5028, 65 27.86 31.34 11.14- - 3.045.908.0 11.14 1.671.821.771.72 1.67 1.88

57 6 G) 302

The mixtures are made on laboratory mechanical tests of the mixtures and volcaval coats, vulcanized in hydraulic lows are summarized in table. 3

ramykh presses. Physical Plasticity Results

according to Carrera

+ 70 ° С, conventional

Flour Viscosity + 100 ° C, 32323124 conv. ets. Podvulcanization time + 121 ° С, min. 19 209 1922 Optimum of vulcanization + 150 ° C, min. 4 353535 Tear resistance, MPa 22.4 22.0 Voltage at 300%, elongated. , nenii, MPa10,1 10,6 Relative elongation at break,% 524 515 Residual elongation. "Nenie when different. ditch,% 3332 Hardness on TM-2, sr. units 60 .54 Elasticity by rebound,% 35 36 37 38 Tear resistance 114 112 92 tear, kn / m Brittleness temperature, from -60 -6О -60 -6О Coefficient of heat aging 120 ° С X 24 h on the other, 7О О, 72 О, 68О, 61 nosti on relative lengthening 0,42 0,43

Table 3

O, 39 O, 43 O, 38 O, 44 O.45 0.51 0.38

41 20.2 16.6 7.3 6D 564 560 33 30 5O 46 O, 35 O, 32 37272722 182O2122 404O45 4.2 23.6 23.0 21.3 25.4 11.5 8.8 9.3 6.7 11.9 34 588 572 604 518 32 32 34 38 32 61 58 6О 52 62 32 31 31 30 35 127 123 123 115 14О -56 -56 -56 -55 -55 -59 O, 55 O, 57 0, 32 0.29

, 1,151.14 1, O7 0.97 1.05 0.996 1.02 1, O8 1.14 1.12

Thus, as a result of the use of the hygrocracking base oil in SKI-3 based blends, the following beneficial effects are obtained in comparison with the use of the plasticizer, MO-6:

reduced time to reach optimum vulcanization;

stress value decreases at ZOO% elongation;

hardness decreases and rebound elasticity increases;

the brittleness temperature decreases;

for vulcanizates with the proposed plasticizer, the coefficient of thermal-rubber SKD 60.0658.3156.6655.1O is better. Stearic acid 1,501,461,421.38 Captax 1,201,171,131,10 Zinc oxide 3,002,922,832,75 Soot PM-100 SO, 05.0,1528,3327,55

Continued table. 3

O, 87 1, OO 0.99 .1.22

1.13 1.02 1.05 1.03

HE aging by strength, relative and residual elongations;

in vulcanizates with the proposed plasticizer, the ozone aging coefficient is better in strength and relative. elongation.

Example 2. Preparing mixtures of butadiene rubber-SKD, containing, as plasticizers, a well-known product, oil PN-6 and the proposed hydrocracking base oil.

Recipes for mixtures (v. Weight.%) Are given in table. 4. A control mixture without plasticizer was also made.

Table4 6О, 0658,3156,6655,1О61,92 1,501,461,421,381,55 1,201,171,13 1,101,24 3,002,922,83 2,753.1 ЯО.О529,1528,33 27.55З, 9c;

9 Hydrocracking base oil BMG-25-3.00 5.838.50 Oil MO-B- “Sulfur 1.20 1,171.13

Plastic

according to Carrera .. + 70 ° С, services 0.11 0.11 0.15 0.18 O, 12

82 746496

84

11 121412

ten

 45

45 505045

Resistance

rupture, MPa 12.0 11.2 10.6 9.5 13.1 Stress at ZOO% elongation, 8.1 7.3 5.9 5.1 MPa Relative elongation at time, 394 392 434 462 snout,% Residual elongation at break,%

Hardness

61 535061

T.M-.2, cond. 62

765302

ten

Continued, table. four

O, 17 0.19 0.24 0.07

847865. 100

1314 169

OO 55O

12.0 11.8 11.0 13.2

64

59 56 50 11.02 3, OO 5.83 8.50 11.02 1.10 1.20 1.17 1.13 1.1O 1.24 7.0 5.7 6.4 3.7 9, 9 406 474 498 594 358 778

765.ZO2

eleven

Elasticity

by rebound,% 4747 4544 44

Resistance

rend, kk / m4547 4549 44

Brittleness temperature, t

-75-76 -75 -75 -69 Thermal aging coefficient 120 Cx; 24 hours by by-set 0.68 O, 71 O, 69 O, 61 by relative elongation 0.37 0.39 0.36 0.30

by residual

elongation 1, OO 0.5 0.13 O Dynamic endurance, thou. C ({CLR repeated stretching 9О64 14-27-30-667 -116-278 Ozone aging coefficient by the wavelength, 1.21 1, О8 1, OO O, 96 relative elongation 1, O5 O, 98 1.01 0.82

Thus, as a result of the use of a hydrocracking base oil in mixtures based on SCD, the following positive effects are obtained in comparison with the use of the well-known plasticizer PN-6:

reduced flour by flour;

reduced time to achieve optimum vulcanization;

rebound elasticity increases;

12

Continued table. five

46 44 4348

4554 6248

-69 -69 -69-7O

O0.14 O 0.14

ABOUT

brittleness temperature decreases; heat aging coefficients for relative strength and residual elongation are improved

ozone aging coefficients for strength and relative elongation are improved.

Example 3. Preparing mixtures of SKMS-ZO-ARKL-15 butadiene-styrene rubber containing, in caO, 580.61 O, 58 O, 61 0.58 0.35 O, 34 O, 31 0.34 0.35 87- 51 - 41-5O- 6249 866 -533 -714 -104 O, 9O 1.05 1, OZ 1, OO 1.05 0.87 1, O8 1.20 1.15 0.99

i376530214

HOCTBtt shlactifkato) a well-known oil-recipe mixtures (in weight) is given

PN-6 and the proposed - base oils table. 6. A contact hydrocracking mixture was also produced without plasticizer. SKMS60 rubber, 31 58.5556.8855.31 -ZOZA ARKM 15 Stearinova 1.21 1,171,141.11 acid 0.90. 0.880.850.83 Altax Diphenylguan0, 18 0.170.170.16 din 3.02 2.932.842.77 Zinc oxide 30.16 29.2728.4427.65 Soot PM-100 Base hydrocracking oil 3.02 5.858.5311 About BMG-15 Oil PN- 6 1.21 1.17 1,141.11 Sulfur

The mixtures are made on laboratory rolls, vulcanized in hydraulic presses. Re + 7O С, cond. ets, O, 33 O, 43 O, 48 0.54 Mooney Viscosity + 100 ° C, 47 41 33 27 conv. ea. Time of scorching + 12 ° С, min 10 1О 11 1О

Table 6 - the results of physico-mechanical tests of mixtures and vulcanizates are summarized in table. 7

Table 7 O, 3158.5556.88 55.3162.19 1.211.171.14 1.111.24 6.90 O, 88 O, 85 O, 83 O, 93 0.180,17 O, 17 0.16 0.19 3, O22,932.84 2.77 3.11 DA, 1629 2728.44 27.6531.09 - -3, O25.85 8.53 11, About 1.211.17 1.14 1, O, 43 O, 46 O, 50 O, 51 0.38 47 4О 35 32 46 1О Ю 1О 11 9 Optimum vulcanization + 143С, min 65707О 75 Resistance 17.7 18.7 18.1 16.2 rupture, MPa Stress at ZOO% elongation 12, 9 11, 6 9.1 7.4% MPa Elongation at break,% 384 430 482 50О

Residual elongation at break,%

Hardness TM-2, sm. ed

Rebound elasticity,%

Tear resistance, kN / m

The brittleness temperature, with a coefficient of thermal aging, 120 ° x 24 h 0.91 O, 79 O, 80 0.85 in strength by relative elongation 0.67 0.55 0.54 0.584 in residual elongation0.4 0.42 0, 5 O, 53 Diyamichesky endurance, thousand cycles of repeated stretching 1466 2314 3548 3819 65757580 19.4 19.0 19.2 18.6 22.0 12.8 12.1 8.9 5.614.9. 408 438 508 630422 0.82 0.76 0.81 O, 70 0.80 0.66 0.52 0.58 0.51 0.64 0.4 O 0.33 0.5 O, 40 0.33. . 2276 3172 3510 2044 3008

17 Coefficient of ozone aging by strength 1.11 1D5 1.62 1.12 by relative elongation 1, 02 0.47 1.07 1, O6

Thus, as a result of the use of hydrocracking base oil in mixtures based on SCMS-AO RCM-15, the following beneficial effects are obtained in comparison with the known plasticizer PN-6:

slightly less Mooney viscosity;

less tear resistance;

less residual elongation;

less hardness and higher elasticity;

5.5 8.0 10.4

2.8

7653О2

18 Iroa table. 7

lower brittleness temperature;

Higher thermal aging coefficients for strength, relative and residual elongation, higher coefficients of ozone aging for strength and relative elongation.

Example 4. Preparing mixtures of butyl rubber containing as a plasticizer: known - oil stabiloyl-18 and the proposed oil - hydrocracking base oil. A control blend without plasticizer was also produced (see tab. 8).

Table 8

5.5 8.0 10.4

2.8 1.09 1.12 1.24 O, 96 0.82 0.88 O, 97 O, 85 0.94 0.94

1976530220

The mixtures are made in lag) orato |: compost 12 - hatching; l.o Berezheni metric mixer on the temperature of the mixture and / in

Aurf in the following mode: first

All the ingredients of the station, except for the volcanic-C-mixture, will vulcanize in 1

Zutoschuyu group and volcanic accelerators-5 presses. Results fnzyk-

organizations; 3.5 mixing to the temperature of mechanical testing of vulcanizates

mixtures n / n. The second stage is summarized in table. 9. cond. units + 70 C 0.34 0.45 0.50 O, 54

Viscosity

Muni + 10 ° C

conv. ed.747

35

99

ten

Optimum vulcanization + 170 ° C, min5

10 15

1212 10

7 Elongation at. rupture,% 41О 456 470 509 Residual elongation at break,% 34323О28 Hardness in TM-2, used units. 85 696565 Elasticity 12, 17 by rebound,% 9 Tear resistance, kN / m57 59 565 O Brittleness temperature, ° C -52 -54

Table 9

328857 4938 107

12 9

1O1010 10

1O67895

11 1717 1514. 17

3.3 6.2 5.24.9 9.3

6

42 38 -56 0.31 0.43 0.48 0.51 0.25 498 538 609 637 496 49 4443 95868382 96 10 8 5053 57 61 -49 -50-50 -51-48 0.85 O, 89 0 , 82 0.83 0.68 in relative elongation O.aO 0.78 O, 75 0.74 in residual elongation O, 66 0.80 0.85 O, 88 Dynamic endurance,, thousand cycles of repeated stretching 5825 ZOOO 2980 244O Coefficient of ozone sta-durability O, 99 0.99 0.99 1, OO by relative elongation O, 96 0.97 0.99 1, OO

Thus, the use of hydrocracking base oil in butyl rubber based mixtures provides the following beneficial effects in comparison with the known plasticizer stabiloyl-18:

better plastoelastic plasticity, Carrell properties and Mooney viscosity;

less tear resistance;

less than the value of residual elongation;

Ethylene propylene rubber 61.1

Sulfur0.16

Peroxide2,14

Zinc White3.05

Soot30,5

lower hardness and more elasticity} lower brittleness temperature; higher rates of thermal aging in strength, relative and residual elongation.

Example 5. Preparing mixtures of ethylene-propylene rubber - SKEP-2-50, containing known as plasticizer - oil VNIINP-BA-8 and proposed - base oil of hydrocracking (see Table 1O).

Table 1O

57.0561,159,357,65

0,150,160,150,15

2, O12,142, O72, O1

2.87 3,052,962,87

28.7 30.529.628.7 0.65 0.72 0.68 O, 67 0.50 0.25 0.23 O, 23 O, 22 0.21 15221 10766 8269 5O7O 15120. 0.99 O, 99-1, OZ 1,070.95 -0.98: O, 91 O, 99 0.98 O, 98O, 97

Ingredients

3.05 5.92 8.62 Production of mixtures is carried out on laboratory rollers. Vulcanization is carried out with 15 leads in hydraulic frame presses

+ 7O С-cond. units O, 54 O, 57 O, 59 O, 54 O, 57 0.58

877361837364

323340293233 11.6 10.0 7.2 12.3 10.6 8.1

16.0 14.5 14.0 16.0 15.3 15.1 42545О 560 416 47О 540

Residual elongation at break,%

Resistance

rend, kn / m5247 51485051

Elasticity

by rebound,% 5251 5252 5152

Mixes

   plf p 5 T 6

3, O5 5.92 8.62

eight

eight

10 12

10 electrically heated. The results of physico-mechanical tests of mixtures and vulcanizates are summarized in table. 11. Table 11

25

The coefficient of thermal aging 1OO ° C X 72 h strength

relative elongation

Ozone resistance coefficient 0.96

13.8 15.0 47.5 7.7 1O, 3 33.8

Temperature

-69 fragility, G

Thus, as a result of using hydrocracking base oil in mixtures based on EPDM 2-5O, the following beneficial effects are obtained in comparison with the known VNIINP-VL-8 plasticizer:

Better indicator of scorching time with, which will increase the safety of their processing in industry and in comparison with the known ones;

less stress at ZOO% elongation;

lower hardness;

better heat aging performance;

better on ozone aging;

better performance in dynamic endurance.

76S3O2

26 Continued gab. eleven

1.00 1.04 0.99 1.01 0.98

0.94 1.02 0.95 0.95 O, 97

O, 99 O, 98 O, 87 O, 93 O, 96

1.01 O, 99 0.94 O, 9O O, 88

-72 -69-70 -70

-70

Of the examples presented, the advantages of hydrocracking base oils as a plasticizer for non-polar, high-density and low-unsaturation non-polar ugly rubber, are clearly evident in comparison with the plasticizers currently used for them: PN-6, stable-18 oils. VNIINP-VA-8 for a number of indicators:

lower Flour viscosity;

less hardness and higher elasticity;

better low-temperature properties, in particular the temperature of brittleness;

higher thermal aging coefficients for strength, relative and residual elongation; higher indicators for resistance to corrosion, both in strength and in relative muscle resistance; in the vulcanizates of the proposed mixture based on low concession rubbers (EPDM and BK), the value of the residual elongations at break is lower; the vulcanizates of the proposed mixture on the basis of EPDM higher indicators of dynamic endurance; the proposed mixtures on the basis of low indiscretion rubbers have better plastic properties. formula of the invention Rubber mixture based on a non-no. rubber, dispersant, vulcanization agent, vulcanizing agent, vulcanization accelerator, filler and plasticizer, characterized in that, in order to improve frost resistance, the physicomechanical the plasticizer mixture contains a hydrocracking base oil with a kinematic viscosity of 3.5-25 eats at + 5 ° C in the following ratio of components, wt.%: Rubber55,10-62.70 Disperser 1.11-1.70 Volcanic activator 1, 67-3, 11 ores Curing agent 1.10-2.4 9 Volcanic Accelerator0, 84-2.71% of Base Oil Hydro2, 80-11.14 Cracking Filler Else Information sources taken into account during the examination 1. Plasticizers and protective agents from petroleum. Ed. Lukayevich I., P. M., Khimi, 1970 p.4O, 59 (prototype).

Claims (2)

Claim Non-polar rubber compound, including dispersant, vulcanization activator, vulcanizing agent 20, vulcanization accelerator, filler and plasticizer, characterized in that, in order to increase frost resistance, physicomechanical and operational properties of rubbers from this mixture, as well as reduce the cost of the latter , as a plasticizer, the mixture contains a hydrocracking base oil with a kinematic viscosity of 3.5-25 cst at +50 C in the following ratio of components wt.%: Rubber 55.10-62.70 Dispersant 1.11-1.70 Vulcanization activator Vulcanizing agent vulcanization accelerator Hydrocracking Base Oil Filler 1.67-3.11 1.10-2.49 0.84-2.71 2.80-11.14 Rest